CN105289734B - A kind of method of the metallic organic frame films degradating organic dye based on metalloporphyrin - Google Patents
A kind of method of the metallic organic frame films degradating organic dye based on metalloporphyrin Download PDFInfo
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- CN105289734B CN105289734B CN201510714071.2A CN201510714071A CN105289734B CN 105289734 B CN105289734 B CN 105289734B CN 201510714071 A CN201510714071 A CN 201510714071A CN 105289734 B CN105289734 B CN 105289734B
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Abstract
The invention discloses a kind of method of the metallic organic frame films degradating organic dye based on metalloporphyrin, it is characterised in that：Porphyrin metal organic frame film is generated in clear glass sheet surface, network is placed in this and is suspended from organic dye solution, at room temperature, it is seen that luminous intensity 300w irradiates 1 4h, organic dye solution is degraded to the concentration that can be discharged；Prepared by metallic organic frame films based on metalloporphyrin is characterized in, by by the pretreated clear glass thin slice of 3 aminopropyl triethoxysilanes (APTMS) respectively with to carboxyl tetraphenyl manganese (or iron/cobalt) porphyrin, containing Zn2+Solution and 2, the bipyridyl of 2 ' dimethyl 4,4 ' dipping bubble reaction, complete single-steeping circulation after, with solvent washing, repeat impregnation steps, the thickness of film is by circulating dipping time control；Oriented and ordered, the porous porphyrin metal organic frame films prepared.The single or mixture solution that the present invention forms metallic organic frame films for light degradation methylene blue, methyl orange, rhodamine, catalytic effect is good, recycling is convenient, is a kind of good new material for being alternatively used for degradation of organic dyes.
Description
Technical field
The present invention relates to a kind of metallic organic frame films material oriented and ordered, that film thickness is controllable based on metalloporphyrin to drop
The method for solving organic dye waste water.
Background technology
Metal-organic framework material (metal-oraganic frameworks, abbreviation MOFs) is as a kind of new more
Hole inorganic-organic hybridization crystalline material, cause extensive concern in fields such as chemistry, material, physics.MOFs, also referred to as polycomplexation
Compound, it is a kind of using metal ion or metal ion cluster as node, with passing through coordinate bond containing carboxylic acid or nitrogenous organic ligand
Mode self assembly and form the network frame crystalline material of periodic arrangement.MOFs combines the characteristics of inorganic and organic material,
There is composition and structure diversity, specific surface area is big and bore hole size, surface chemical property are adjustable, deposited in gas
Store up with separating, lighting, sensing, being catalyzed, the field such as magnetic has extensive potential using value.When MOFs is produced the shape of film forming
During formula, MOFs materials are expanded the very big application in gas/liquid phase field, at the same be advantageous to the devices of MOFs materials with
And the reduction of use cost.MOF films have great application value in fields such as gaseous jet simulation, detection of gas and Membrane catalysis
With development space.
At present, existing a variety of methods prepare MOF films, such as microwave induced heat deposition, dip coated, electrochemical deposition, electricity
Swimming deposition, LbL methods and solvent-thermal method.Most notably LbL methods, it is alternately by structure block liquid deposition to functionalization base
On plate, ultra-thin, orientation and the adjustable MOF films of thickness have been obtained.The MOF film preparations of porphyrin and metalloporphyrin are difficult, relevant report
Seldom.Recently, Joseph T.Hupp etc. are prepared for the MOF films based on porphyrin using LbL method on silicon plate first
(J.Am.Chem.Soc., 2013,135,15698), but its report two kinds of porphyrin MOF films on its horizontal plane do not include have
The metalloporphyrin not being coordinated, i.e. prepared porphyrin film do not have catalytic active site.In recent years, existed on porphyrin or metalloporphyrin
The report of film forming on substrate, all it is that the coordination link of metalloporphyrin central metallic ions increases mostly, or passes through porphyrin outer shroud
Carboxyl link increases, or the growing film by way of π-pi-conjugated growth.And synthesized directly on substrate by LbL methods
Had not been reported on horizontal bedding containing the metalloporphyrin MOF films not being coordinated.And utilize the transparent metal with catalytic active site
The technology of porphyrin MOF film photocatalytic degradation of dye waste water is even more to have no report.
The content of the invention
The invention provides a kind of method of MOF membrane materials photocatalytically degradating organic dye, using directly with transparent base
The MOF films based on metalloporphyrin in active site are photochemical catalyst on the horizontal plane synthesized on plate, are shone in normal temperature, visible ray
Under conditions of penetrating, catalytic degradation is carried out to the common solution containing methylene blue, methyl orange, rhodamine, had simple, high
The characteristics of imitating, be practical.
In method provided by the invention, the technology of preparing scheme for the metalloporphyrin MOF films of degradating organic dye is as follows：
1) pretreatment of carrier.Cleaned successively with cleaning fluid, deionized water, acetone, ethanol, deionized water sonic oscillation
Bright glass carrier 20 minutes, then with the Piranha solution (H of brand-new2SO4:30% hydrogen peroxide=3:1, v/v) in 90 DEG C of leachings
1h is steeped, is then rinsed with substantial amounts of ultra-pure water, in high pure nitrogen after drying, then in 100 DEG C of oven for curing 0.5h, obtains hydroxyl
The substrate of base.Substrate after hydroxylating is immersed into the 3- aminopropyl trimethoxysilanes (APTMS) newly configured and absolute ethyl alcohol
Mixed liquor (volume ratio 1：15), shaking reaction round the clock, is then cleaned with EtOH Sonicate on shaking table, with deionized water rinsing simultaneously
Drying.The reaction obtains the substrate of surface amination processing after terminating.
2) solution is prepared.By zinc acetate, 5,10,15,20- tetra- to carboxyl phenyl manganoporphyrin and 2,2'- dimethyl -4,4'-
Bipyridyl is dissolved in ethanol solution that concentration is made is respectively 0.1mmol/L, 2 μm of ol/L and 2 μm of ol/L respectively.
3) film preparation.Pretreated substrate is separately immersed in the above-mentioned solution prepared successively, every time before immersion
All rinsed with alcohol solvent, remove unreacted residual ion, make each immersion process all only have a molecular layer to participate in reaction,
Mode of operation such as Fig. 1.
The catalysis material (as shown in Figure 2) of sheet glass load porphyrin MOFs films prepared by the present invention, has translucency,
The film of both sides can play catalytic action, can fully receive the visible ray of irradiation, efficient photocatalytically degradating organic dye occurs
The reaction of waste water, recycling is convenient, catalytic effect is good, is a kind of alternative for the good new of degradation of organic dyes
Material.
Brief description of the drawings
Fig. 1 is the schematic diagram (by taking manganoporphyrin as an example) that the present invention prepares metallic organic frame films layer by layer, and Fig. 2 is that sheet glass is born
Carry the color contrast before and after metalloporphyrin MOFs films.
Embodiment
The present invention program is illustrated below, but the present invention includes but is not limited to examples below：
Embodiment 1
Glass substrate (2x3cm) after APTMS is handled is successively respectively in zinc acetate (0.1mmol/L), 5,10,15,20-
40 DEG C in the ethanol solution of four pairs of carboxyl phenyl manganoporphyrins (2 μm of ol/L) and 2,2'- dimethyl -4,4'- bipyridyls (2 μm of ol/L)
10~12min of lower immersion, washed every time before immersion with ethanol, one circulation of immersion is a growth cycle, soaks 7 circulations
Obtain the MnPor-MOF that grown a 7 layers film.It is placed on network and is suspended from aqueous solution of methylene blue (4 × 10- 5Mol/L, 50ml), first avoid light place 30min, catalyst is reached adsorption-desorption balance in reaction solution.Then with 300W's
Xenon arc light irradiation glass substrate, H2O2With the catalysis photodissociation system of methylene blue.When determining different irradiations by UV-vis spectrometers
Between the change of absorbance of the methylene blue at 665nm represent the palliating degradation degree of methylene blue, react methylene after 180min
The blue degradation rate of base has exceeded 93%.
Embodiment 2
Glass substrate (2x3cm) after APTMS is handled is successively respectively in zinc acetate (0.1mmol/L), 5,10,15,20-
40 DEG C in the ethanol solution of four pairs of carboxyl phenyl Cob altporphyrins (2 μm of ol/L) and 2,2'- dimethyl -4,4'- bipyridyls (2 μm of ol/L)
10~12min of lower immersion, washed every time before immersion with ethanol, 14 circulations of immersion obtain a CoPor- that grown 14 layers
MOF films.It is placed on (4 × 10 in the rhodamine B aqueous solution-5Mol/L, 50ml), then with 300W xenon arc light irradiation glass base
Plate, H2O2With the catalysis photodissociation system of rhodamine B.Represented by the change of the absorbance at UV-vis spectrometers measure 554nm
Palliating degradation degree, the bright degradation rates of Luo Dan B have exceeded 95% after reacting 120min.
Embodiment 3
Glass substrate (2x3cm) after APTMS is handled is successively respectively in zinc acetate (0.1mmol/L), 5,10,15,20-
40 DEG C in the ethanol solution of four pairs of carboxyl phenyl manganoporphyrins (2 μm of ol/L) and 2,2'- dimethyl -4,4'- bipyridyls (2 μm of ol/L)
10~12min of lower immersion, washed every time before immersion with ethanol, one circulation of immersion is a growth cycle, and immersion 14 follows
Ring obtains the MnPor-MOF that grown a 14 layers film.It is placed on methylene blue (1 × 10-5Mol/L), rhodamine B (1 ×
10-5Mol/L), methyl orange (2 × 10-5Mol/L) (50mL) in mixture solution, then with 300W xenon arc light irradiation catalytic body
System, the change of the absorbance at 665nm, 554nm and 464nm is determined respectively by UV-vis spectrometers to represent palliating degradation degree,
Degradation rate is respectively 96%, 95%, 97% after reacting 120min.
Embodiment 4
MnPor-MOF films after reaction in embodiment 1 is terminated are taken out, and with the multiple washes clean of deionized water, vacuum is done
Re-use after dry, reacted under the same terms of example 1, after recycling 5 times, the degradation rate of methylene blue also can reach
More than 85%.
Above example illustrates that the organic metal porphyrin film has active site, and film thickness is controllable, returns
Receive simple and reusable, the industry available for processing containing methyl orange, methylene blue, rhodamine B etc. similar to chemical constitution
Organic dye waste water.
Claims (2)
- A kind of 1. method of the metallic organic frame films degradating organic dye based on metalloporphyrin, it is characterised in that：In transparent glass Glass sheet surface generates porphyrin metal organic frame film, is placed in network with this and is suspended from organic dye solution, at room temperature, Visual intensity 300w irradiates 1-4h, organic dye solution is degraded to the concentration that can be discharged；The film catalyst material system used Standby process is, by by the pretreated clear glass of 3- aminopropyl triethoxysilanes (APTMS) successively with containing Zn2+It is molten Liquid, carboxyl tetraphenyl metalloporphyrin and 2,2 '-dimethyl -4,4'-Bipyridine dipping bubble reaction, completion single-steeping are circulated Afterwards, with solvent washing, impregnation steps are repeated, the thickness of film is by circulating dipping time control；That prepares multi-layer oriented has Sequence, porous porphyrin metal organic frame, not soluble in water and benzene, ether, chloroform, dichloromethane, methanol and ethanol common solvent, It is stable in the air；The film is due to column-supporting agent 2, the steric hindrance of 2 '-dimethyl -4,4'-Bipyridine, in an assembling process not Axial coupling can be formed in the metal ion center of metalloporphyrin, so as to retain the activated centre position of metalloporphyrin so that prepare The organic frame film gone out has very strong photocatalytic activity；In used metalloporphyrin its metallic atom be manganese, iron, cobalt its Middle one kind.
- 2. based on the method described in claim 1, its organic dye solution used is methylene blue, methyl orange, rhodamine B shape Into single or mixture solution.
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| CN112210787B (en) * | 2020-09-28 | 2022-01-14 | 西南石油大学 | Preparation method of metal organic framework material coating on surface of nano-structure substrate |
| CN113150298B (en) * | 2021-03-31 | 2022-04-22 | 南通大学 | Covalent organic polymer based on porphyrin and preparation method and application thereof |
| CN115558118B (en) * | 2022-02-22 | 2023-07-07 | 中国科学院上海硅酸盐研究所 | Two-dimensional metal organic framework nano sheet with catalytic oxidation resistance, and preparation method and application thereof |
| CN115216023B (en) * | 2022-05-19 | 2023-07-25 | 山东大学 | Iron-based MOFs material with photo-thermal conversion performance and preparation method and application thereof |
| CN115672396B (en) * | 2022-10-26 | 2024-03-08 | 西安工程大学 | Preparation method of glass-based porphyrin film photocatalyst |
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